CN104231952A - Adhesive film for polarizing plate, polarizing plate and optical display - Google Patents
Adhesive film for polarizing plate, polarizing plate and optical display Download PDFInfo
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- CN104231952A CN104231952A CN201410279652.3A CN201410279652A CN104231952A CN 104231952 A CN104231952 A CN 104231952A CN 201410279652 A CN201410279652 A CN 201410279652A CN 104231952 A CN104231952 A CN 104231952A
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J133/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
- C09J133/04—Homopolymers or copolymers of esters
- C09J133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
- C09J133/08—Homopolymers or copolymers of acrylic acid esters
-
- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B5/00—Optical elements other than lenses
- G02B5/30—Polarising elements
- G02B5/3025—Polarisers, i.e. arrangements capable of producing a definite output polarisation state from an unpolarised input state
- G02B5/3033—Polarisers, i.e. arrangements capable of producing a definite output polarisation state from an unpolarised input state in the form of a thin sheet or foil, e.g. Polaroid
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J133/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
- C09J133/04—Homopolymers or copolymers of esters
- C09J133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
- C09J133/062—Copolymers with monomers not covered by C09J133/06
- C09J133/066—Copolymers with monomers not covered by C09J133/06 containing -OH groups
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J7/00—Adhesives in the form of films or foils
- C09J7/10—Adhesives in the form of films or foils without carriers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2314/00—Polymer mixtures characterised by way of preparation
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J2203/00—Applications of adhesives in processes or use of adhesives in the form of films or foils
- C09J2203/318—Applications of adhesives in processes or use of adhesives in the form of films or foils for the production of liquid crystal displays
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J2301/00—Additional features of adhesives in the form of films or foils
- C09J2301/30—Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier
- C09J2301/312—Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier parameters being the characterizing feature
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J2433/00—Presence of (meth)acrylic polymer
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Physics & Mathematics (AREA)
- General Physics & Mathematics (AREA)
- Optics & Photonics (AREA)
- Polarising Elements (AREA)
- Adhesives Or Adhesive Processes (AREA)
- Adhesive Tapes (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
An adhesive film for a polarizing plate is disclosed. The adhesive film includes a cured product of a composition including a (meth)acrylic copolymer and a cross-linking agent, and has a peel strength ratio of about 6 or more, as represented by Equation 1. An adhesive composition for the adhesive film, a polarizing plate including the adhesive film, and an optical display including the adhesive film are also described.
Description
Technical field
The application relate to for polarization plates binder film, comprise it polarization plates and comprise its optical display.
Background technology
Polarization plates is provided at the upper side and lower side of liquid-crystal display (LCD) panel and bonds on the lcd panel by the binder film for polarization plates.Described polarization plates is shunk or is expanded under the severe condition of high temperature (such as, 85 DEG C) and high humidity.Here, if the binder film for polarization plates presents poor weather resistance, then polarization plates from LCD peel off and therefore suffer such as to depart from, the fault such as foaming, and due to polarization plates and for polarization plates binder film between dimensional change difference also can cause light leak.Therefore, binder film needs high-durability and by controlling or alleviate pressure that the contraction or expansion due to polarization plates causes and suppressing the performance of light leak.In addition, binder film should present the good stripping ability again for reprocessing, described reprocessing is carried out due to the foreign matter when the polarization plates comprising binder layer being adhered on the lcd panel or machining failure, and binder film also presents good cutability and short aging time can use after coating adhesive very soon to make it, thus improves the productivity of polarization plates.
Although the gravity die binder film for the over-curing of polarization plates is highly cross-linked after aging and therefore suppress light leak, the gravity die binder film of described over-curing can suffer because low initial adhering force is in the disengaging of the edge of described polarization plates or wrinkling.Depend on the content of linking agent, between weather resistance and light leak, there is trade-off relationship.If reduce the content of linking agent, although produce good weather resistance due to low cross-linking, polarization plates can suffer serious light leak, if increase the content of linking agent, although light leak is suppressed, and can the weather resistance of deteriorated polarization plates.
Summary of the invention
According to an aspect of the present invention, the binder film for polarization plates can be formed by the composition comprising (methyl) acrylic copolymer and linking agent.And have the stripping strength ratio of about 6 or larger, described stripping strength is than being represented by equation 1:
[equation 1]
Stripping strength ratio=B/A (limiting A and B as described in detail below)
According to another aspect of the present invention, polarization plates can comprise the above-mentioned binder film for polarization plates.
According to a further aspect of the invention, optical display can comprise above-mentioned polarization plates.
Accompanying drawing explanation
Fig. 1 is the viewgraph of cross-section of the polarization plates according to an embodiment of the invention;
Fig. 2 is the viewgraph of cross-section of the optical display according to another embodiment of the present invention.
Embodiment
As used herein, the term of such as " above " and " below " is limited with reference to accompanying drawing.Therefore, term " above " can be understood can exchange with term " below " and use.In addition, term " (methyl) acrylate " can refer to acrylate and/or methacrylic ester.
After this, the binder film being used for polarization plates according to the embodiment of the present invention will be described in detail.
According to an embodiment of the invention; binder film for polarization plates can be used for polarization plates to be connected to display panel; wherein; described polarization plates can comprise: polarizer; with the blooming be formed on one or two surface of described polarizer; and described blooming can be protective membrane or optical compensation films, and described panel can be the panel of such as liquid-crystal display.
Usually, because polarization plates comprises the polarizer and blooming presenting different physical characteristics, and described polarizer is the film stretched in one aspect, and polarization plates is collapsible or expand under the severe condition of high temperature and/or high humidity.Due to this character of described polarizer, described polarization plates can suffer the weather resistance (disengaging, foaming etc.) of light leak and difference.Therefore, binder film for polarization plates needs the pressure that can cause by controlling or alleviate the contraction or expansion due to polarization plates to control the performance of light leak, and prevents polarization plates under high temperature and/high humidity, suffering such as to depart from the performance of the fault such as liquid crystal cell, foaming.The invention provides the gravity die binder film that can be suppressed light leak by the pressure controlled because the contraction or expansion of polarization plates causes.Known compared with soft-type binder film, due to the low wettability under high temperature and/or high humidity, described gravity die binder film can suffer the deterioration of stripping strength usually.
According to an embodiment of the invention, although be gravity die binder film for the binder film of polarization plates, described binder film has the stripping strength ratio of about 6 or larger, and described stripping strength is than being represented by equation 1.As a result, described binder film presents good weather resistance due to the good wettability under high temperature and high-peeling strength, and prevents described polarization plates from suffering light leak by controlling the pressure that caused by the pucker & bloat of polarization plates.
[equation 1]
Stripping strength ratio=B/A
Wherein, A be when at 25 DEG C with the angle of 180 ° and use 30kgf load sensor to be peeled off from glass substrate by described binder film with the draw speed of 300mm/min time stripping strength (unit: gf/25mm); And B be when by described binder film 85 DEG C place 60 minutes then at 85 DEG C with the angle of 180 ° and use 30kgf load sensor to be peeled off from glass substrate by described binder film with the draw speed of 300mm/min time stripping strength (unit: gf/25mm), described stripping strength ratio measured by sample glass substrate being wherein formed with the polarization plates comprising described binder film.
If described stripping strength ratio is less than 6, when the panel comprising connected polarization plates is placed under high temperature and/or high humidity, described polarization plates can suffer due on its edge wrinkling or the deterioration or the light leak that depart from the weather resistance caused.In one embodiment, described binder film can have the stripping strength ratio of such as about 6 to about 20, particularly, and about 6,7,8,9,10,11,12,13,14,15,16,17,18,19 or 20.Stripping strength also can be measured according to JIS2107.Such as, be used for the binder composition of polarization plates by coating in polarization plates, under the fixed temperature and humidity conditions of 35 DEG C and 45%RH (relative humidity) aging 2 days subsequently, and for the preparation of measuring the sample of stripping strength.Here, polarization plates is prepared by stacking triacetyl cellulose (TAC) protective membrane on two surfaces of polarizer.
For described binder film, A can in the scope of about 200gf/25mm to about 500gf/25mm, such as, in the scope of about 200gf/25mm to about 350gf/25mm, and B can about 1500gf/25mm to about 3000gf/25mm scope in, such as, about 1590gf/25mm to about 3000gf/25mm scope in, such as, in the scope of about 1900gf/25mm to about 3000gf/25mm.Within the scope of this, described binder film can have according to stripping strength ratio of the present invention, and described polarization plates can present good weather resistance under high temperature and/or high humidity.
As represented by equation 2, the binder film for polarization plates can have the gel fraction (degree of crosslinking) of about 70% or more, such as, about 75% or more, such as, about 75% to about 90%.Within the scope of this, described binder film has high crosslink density and therefore effectively can suppress light leak.
[equation 2]
Gel fraction (%)=(W3-W1)/(W2-W1) × 100
(W1 is the weight of wire cloth;
W2 is the gross weight of wire cloth and tackiness agent, and described gross weight is used for the binder composition 3 minutes of polarization plates by dry at 120 DEG C and placed described binder composition 1 hour under 35 DEG C and 45%RH, is then placed on wire cloth and obtains; And
W3 is the gross weight of wire cloth and tackiness agent, wherein will be used for the binder composition 3 minutes of polarization plates and the tackiness agent placement of placing described binder composition 1 hour under 35 DEG C with 45%RH and obtaining is placed in sample bottle on a wire mesh and by described tackiness agent together with described wire cloth by dry at 120 DEG C, ethyl acetate is added subsequently in described sample bottle, then place 1 day at 25 DEG C, at 100 DEG C dry 12 hours subsequently, and obtain described gross weight)
In addition, the described binder film for polarization plates is gravity die binder film and has high storage modulus.Described binder film can to have at 30 DEG C about 5 × 10
5pa is to about 9 × 10
5the storage modulus of Pa, such as, about 6.5 × 10
5pa is to about 7.5 × 10
5pa, the measurement from 0 DEG C to 120 DEG C under 10% strain and 10Hz frequency of described storage modulus.Within the scope of this, described binder film can realize the effective suppression to light leak.
Usually, gravity die binder film can have as represented by equation 2 about 70% or more gel fraction, and about 5 × 10
5pa is to about 9 × 10
5the storage modulus of Pa, and soft-type binder film can have as represented by equation 2 be less than 70% gel fraction, and be less than about 5 × 10
5the storage modulus of Pa.
In addition, the binder film for polarization plates is gravity die binder film and has about 60 μm or less creep(ing) distance, such as, and about 40 μm to about 50 μm.Within the scope of this, described binder film can realize the effective suppression to light leak.
Binder film for polarization plates can have the thickness of about 5 μm to about 100 μm.Within the scope of this, described binder film can be used for polarization plates.
Binder film for polarization plates is transparent and can has the mist degree of such as about 2% or less at 550nm place, such as, and about 0% to about 1%.
The binder film for polarization plates according to an embodiment of the invention can be formed by the binder composition for polarization plates according to an embodiment of the invention.In one embodiment, binder film was prepared by the described binder composition about 48 for polarization plates aging under about 30 DEG C to about 35 DEG C and about 40%RH to about 45%RH is little up to about 96 hours.
In one embodiment, the binder composition for polarization plates comprises (methyl) acrylic copolymer and linking agent.Here, because (methyl) acrylic copolymer decreases the loss of functional group by main chain and the speed of reaction of functional group being adjusted to when being polymerized similar each other thus decreasing not containing the ratio of the multipolymer of functional group, described (methyl) acrylic copolymer comprises functional group that is evenly distributed and that be connected on described (methyl) acrylic copolymer main chain, and about 1 can be had, the weight-average molecular weight of 000,000g/mol or less.In addition, described linking agent can be the polyisocyanate crosslinking agent of modification and the mixture of metal-chelating linking agent.
(methyl) acrylic copolymer can be and (methyl) acrylic copolymer that be connected to copolymer chain in evenly distributed with predetermined space of reactive functional groups wherein.Include not evenly distributed with predetermined space and the binder film being connected to (methyl) acrylic copolymer in copolymer chain of wherein reactive functional groups owing to presenting poor mobility comprising the height between the part being arranged a large amount of functional group interacts, described binder film has the stripping strength ratio being less than 2, and therefore described binder film can be departed from or wrinkling due to the weather resistance of difference.Described reactive functional groups can comprise hydroxyl, carboxylic acid group etc.
As used herein, term " retention time " is for determining that described reactive functional groups is whether evenly distributed with predetermined space and being connected to (methyl) acrylic copolymer main chain.Described retention time is measured, by the time period that the polarization plates that (methyl) acrylic copolymer is coated with is peeled off from sheet glass when polarization plates being peeled off from sheet glass with the power in pre-determined range.The polarization plates including evenly distributed (methyl) acrylic copolymer of wherein reactive functional groups has short retention time due to the low interaction between described reactive functional groups, and include wherein reactive functional groups do not have the polarization plates of evenly distributed (methyl) acrylic copolymer due to include a large amount of reactive functional groups part between Partial Height interact and there is long retention time.
Particularly, the retention time of about 300 seconds to about 400 seconds can be had according to (methyl) acrylic copolymer of an embodiment of the invention.Within the scope of this, the binder film for polarization plates at high temperature presents high wettability and therefore can have high-peeling strength and present good weather resistance.
Be polymerized by (methyl) Acrylic Acid Monomer introduced containing non-reacted functional group (being once polymerized), subsequently by instillation containing reactive functional groups (methyl) Acrylic Acid Monomer (after polymerization), and preparation comprises evenly distributed and connects (methyl) acrylic copolymer of the reactive functional groups on it.When by being polymerized with speed instillation (methyl) Acrylic Acid Monomer containing reactive functional groups in pre-determined range, owing to not introducing (methyl) Acrylic Acid Monomer containing reactive functional groups at once, because this reducing the loss of reactive functional groups, thus allow described reactive functional groups evenly distributed.When (methyl) Acrylic Acid Monomer of mixing containing non-reacted functional group and (methyl) Acrylic Acid Monomer containing reactive functional groups are to be polymerized simultaneously, obtaining wherein reactive functional groups does not have evenly distributed (methyl) acrylic copolymer.Non-reacted functional group can be alkyl, such as, and C
1to C
20alkyl, is in particular unsubstituted C
1to C
20alkyl, is in particular C
1to C
5alkyl.
Once undertaken by typical copolymer polymerization process with after polymerization, such as suspension polymerization, letex polymerization, solution polymerization etc.Each once can carry out at about 65 DEG C to about 70 DEG C with after polymerization about 6 little of about 8 hours.
By adding reaction initiator polymerization (methyl) acrylic copolymer in monomer mixture.Described initiator can add when being once polymerized and can comprise and is selected from by 2, 2-azo two (2, 4-methyl pentane nitrile), 2, 2'-Diisopropyl azodicarboxylate, benzoyl peroxide, dilauroyl peroxide, the tertiary butyl-(2-ethylhexyl) single peroxycarbonates, tert-pentyl-(2-ethylhexyl) single peroxycarbonates, 1, 1-bis-(t-butylperoxy) hexanaphthene, 1, 1-bis-(t-amyl peroxy) hexanaphthene, t-butylperoxy-3, 5, the own ester of 5-trimethylammonium, 1, 1-bis-(t-butylperoxy)-3, 3, 5-trimethyl-cyclohexane, Potassium Persulphate, Sodium Persulfate, at least one in the group of ammonium persulphate and azo water soluble starter composition, but be not limited thereto.Based on (methyl) Acrylic Acid Monomer containing non-reacted functional group of 100 weight parts, can add the initiator of about 0.001 weight part to about 2 weight parts, such as, about 0.04 weight part is to about 0.1 weight part.Within the scope of this, binder film can present high storage modulus.
(methyl) Acrylic Acid Monomer containing non-reacted functional group can be (methyl) alkyl acrylate containing alkyl, and can comprise containing unsubstituted C
1to C
20(methyl) acrylate of straight or branched alkyl.Such as, (methyl) Acrylic Acid Monomer containing non-reacted functional group can comprise (methyl) methyl acrylate, (methyl) ethyl propenoate, (methyl) propyl acrylate, (methyl) n-butyl acrylate, (methyl) tert-butyl acrylate, (methyl) isobutyl acrylate, (methyl) amyl acrylate, (methyl) Ethyl acrylate, (methyl) 2-ethylhexyl acrylate, (methyl) heptylacrylate, (methyl) Octyl acrylate, (methyl) Isooctyl acrylate monomer, (methyl) vinylformic acid ester in the ninth of the ten Heavenly Stems, (methyl) decyl acrylate and at least one in (methyl) dodecylacrylate, but be not limited thereto.
The content of (methyl) Acrylic Acid Monomer in the total monomer mixture for (methyl) acrylic copolymer containing non-reacted functional group can be about 80 % by weight (wt%) to 99.99wt%, particularly, about 90wt% to about 99wt%, more specifically, about 90wt%, 91wt%, 92wt%, 93wt%, 94wt%, 95wt%, 96wt%, 97wt%, 98wt% or 99wt%.Within the scope of this, binder film can not be bubbled or departed under the condition of test thermotolerance and wet fastness, and can present good can the weather resistance of re-workability and excellence.
(methyl) Acrylic Acid Monomer containing reactive functional groups can comprise (methyl) Acrylic Acid Monomer containing hydroxyl and/or (methyl) Acrylic Acid Monomer containing carboxylic acid group.
(methyl) Acrylic Acid Monomer containing hydroxyl can be the C containing having at least one hydroxyl
2to C
20(methyl) acrylate of alkyl.Such as, (methyl) Acrylic Acid Monomer containing hydroxyl can comprise at least one and be selected from (methyl) vinylformic acid 2-hydroxyl ethyl ester, (methyl) vinylformic acid 4-hydroxy butyl ester, (methyl) vinylformic acid 2-hydroxypropyl acrylate, (methyl) vinylformic acid 2-hydroxy butyl ester, the own ester of (methyl) vinylformic acid 6-hydroxyl, 1,4 cyclohexane dimethanol list (methyl) acrylate, 1-chloro-2-hydroxypropyl (methyl) acrylate, Diethylene Glycol list (methyl) acrylate, 1,6-hexylene glycol list (methyl) acrylate, tetramethylolmethane three (methyl) acrylate, Dipentaerythritol five (methyl) acrylate, neopentyl glycol single (methyl) acrylate, TriMethylolPropane(TMP) two (methyl) acrylate, trimethylolethane two (methyl) acrylate, 2-hydroxyl-3-phenoxy propyl (methyl) acrylate, 4-hydroxycyclopent base (methyl) acrylate, 4-hydroxy-cyclohexyl (methyl) acrylate and cyclohexanedimethanol list (methyl) acrylate, but be not limited thereto.Such as, (methyl) vinylformic acid 2-hydroxyl ethyl ester and (methyl) vinylformic acid 2-hydroxypropyl acrylate can be used.
In the total monomer mixture for (methyl) acrylic copolymer, the content of (methyl) Acrylic Acid Monomer containing hydroxyl is about 0.001wt% to 50wt%, preferred 0.005wt% to 25wt%, more preferably 0.005wt% to 10wt%, also more preferably 0.01wt% to 5wt%, be in particular, 1wt%, 2wt%, 3wt%, 4wt% or 5wt%.Within the scope of this, binder film can not be bubbled or departed under the condition of test thermotolerance and wet fastness, and can present good can the weather resistance of re-workability and excellence.
(methyl) Acrylic Acid Monomer containing carboxylic acid group can comprise at least one be selected from (methyl) vinylformic acid and (methyl) β-acryloxypropionic acid, but is not limited thereto.
In the total monomer mixture for (methyl) acrylic copolymer, the content of (methyl) Acrylic Acid Monomer containing carboxylic acid group is about 0.001wt% to 15wt%, preferred 0.01wt% to 10wt%, more preferably 0.1wt% to 5wt%, be in particular, 1wt%, 2wt%, 3wt%, 4wt% or 5wt%.Within the scope of this, binder film presents the cohesive force of improvement, and therefore can present excellent weather resistance to adhere in polarization plates.
(methyl) acrylic copolymer can have the weight-average molecular weight (Mw) of about 1,000,000g/mol or less, such as, about 500,000g/mol to about 1,000,000g/mol, particularly, about 500,000g/mol, 600,000g/mol, 700,000g/mol, 800,000g/mol, 900,000g/mol or 1,000,000g/mol.Within the scope of this, binder film presents good adhesive power and weather resistance, and effectively suppresses light leak.Weight-average molecular weight is by the be converted calculating of polystyrene in gel permeation chromatography.
(methyl) acrylic copolymer can have the second-order transition temperature of about-43 DEG C to about-35 DEG C.Within the scope of this, binder film can present the weather resistance of improvement.Preferably, (methyl) acrylic copolymer has the second-order transition temperature of about-43 DEG C to about-40 DEG C.
(methyl) acrylic copolymer can have the polydispersity index of about 1 to about 10.Within the scope of this, binder film can guarantee weather resistance nargin.Preferably, (methyl) acrylic copolymer can have the polydispersity index of about 3 to about 7.
(methyl) acrylic copolymer can have the viscosity of about 3000cPs to 5000cPs at 25 DEG C.Within the scope of this, binder composition can be guaranteed can coating.Preferably, (methyl) acrylic copolymer has the viscosity of about 3500cPs to 4200cPs at 25 DEG C.
With solid content meter, (methyl) acrylic copolymer can be about 60wt% to 95wt% described for the content in the binder composition of polarization plates, such as, about 65wt% to 91wt%, such as, about 80wt% to 90wt%, particularly, about 80wt%, 81wt%, 82wt%, 83wt%, 84wt%, 85wt%, 86wt%, 87wt%, 88wt%, 89wt% or 90wt%.Within the scope of this, Technologies for High Speed Coating can be used to be coated with described binder composition.
Linking agent can be the polyisocyanate crosslinking agent of modification and the mixture of metal-chelating linking agent.If be used alone the polyisocyanate crosslinking agent of described modification, binder film can present poor weather resistance and bubbled or depart from, if be used alone described metal-chelating linking agent, polarization plates can suffer light leak because the cohesive force of binder film is not enough.
Polyisocyanate crosslinking agent due to described modification comprise there are some blocked isocyanate bases polyisocyanate crosslinking agent to improve the mobility of (methyl) acrylic copolymer, binder film can be guaranteed wettability and under high temperature and/or high humidity, present the weather resistance of improvement.
By alcohol etc. and such as two or more official can the reaction of multifunctional polyisocyanate crosslinking agent of polyisocyanate crosslinking agent to be prepared the polyisocyanate crosslinking agent of modification by some isocyanate group of end-blocking, described multifunctional polyisocyanate crosslinking agent has at least two isocyanate group, such as, the polyisocyanate crosslinking agent of three or more sense.The example of multifunctional polyisocyanate crosslinking agent can comprise 2, 4-tolylene diisocyanate, 2, 6-tolylene diisocyanate, hydrogenated tolylene diisocyanate, 1, 3-Xylene Diisocyanate, 1, 4-Xylene Diisocyanate, ditan-4, 4 '-vulcabond, 1, 3-bis-(isocyanatomethyl) hexanaphthene, tetramethylxylene diisocyanate, 1, 5-naphthalene diisocyanate, 2, 2, 4-trimethyl hexamethylene diisocyanate, 2, 4, 4-trimethyl hexamethylene diisocyanate, the tolylene diisocyanate adduct of TriMethylolPropane(TMP), the Xylene Diisocyanate adducts of TriMethylolPropane(TMP), triphenylmethane triisocyanate and methylene radical two (phenyl isocyanate), but be not limited thereto.Described alcohol is the C with at least one hydroxyl
2to C
16alcohol, and can be ethanol to Cetyl OH.Such as, can in the difunctionality polyisocyanate crosslinking agent comprising two isocyanate group in end-blocking two isocyanate group one, can one or two in the trifunctional polyisocyanate crosslinking agent comprising three isocyanate group in end-blocking three isocyanate group, and can in the four sense polyisocyanate crosslinking agents comprising four isocyanate group in end-blocking four isocyanate group one, two or three.
Based on (methyl) acrylic copolymer of 100 weight parts, the content of the polyisocyanate crosslinking agent of modification can be about 0.1 weight part to about 20 weight parts, such as, about 11 weight parts are to about 19 weight parts, such as, about 13 weight parts are about 18 weight parts extremely, particularly, and about 11,12,13,14,15,16,17,18 or 19 weight parts.Within the scope of this, binder film can present the weather resistance of improvement, and suppresses light leak.
Metal-chelating linking agent can promote be cross-linked and increase cross-linked speed.Metal-chelating linking agent can be typical metal-chelating linking agent.Such as, metal-chelating linking agent can comprise: as the methyl ethyl diketone coordination compound of the metals such as aluminium, iron, copper, zinc, tin, titanium, nickel, antimony, magnesium, vanadium, chromium, zirconium; With the acetylacetic ester coordination compound of described metal.Particularly, the Chelating agent containing aluminium can reduce the time period of aged binder layer, thus reduces process period.
Owing to comprising metal-chelating linking agent according to the binder film for polarization plates of an embodiment of the invention, described binder film can comprise the metal of predetermined amount.Particularly, described metal can be about 0.1wt% to about 10wt% for the content in the binder film of polarization plates, such as, and about 1wt% to about 5wt%.Within the scope of this, binder film can present the weather resistance of improvement.
Based on (methyl) acrylic copolymer of 100 weight parts, the content of metal-chelating linking agent can be about 0.1 weight part to about 10 weight parts, and preferably about 3 weight parts are to about 5 weight parts, particularly, are about 3,4 or 5 weight parts.Within the scope of this, binder film can present the weather resistance of improvement.
Binder composition for polarization plates can have the polyisocyanate crosslinking agent of the described modification of about 1 to about 6 and the weight ratio of described metal-chelating linking agent, such as, and about 3 to about 6.Within the scope of this, binder film can present excellent weather resistance and less performance change in time.
Except the polymeric polyisocyanate of described modification and metal-chelating linking agent, the binder composition for polarization plates can comprise epoxy, azacyclopropane, trimeric cyanamide, amine, imide or acid amides linking agent further as linking agent.
Based on (methyl) acrylic copolymer of 100 weight parts, the content of linking agent can be about 0.2 weight part to about 30 weight parts, and such as, about 9 weight parts are about 25 weight parts extremely, particularly, and about 16,17,18,19,20,21,22 or 23 weight parts.In addition, with solid content meter, the content of linking agent in binder composition can be about 4wt% to about 40wt%, such as, and about 5wt% to about 40wt%, such as, about 10wt% to about 20wt%.Within the scope of this, polarization plates can present less light leak and high-durability.
Binder composition can comprise silane coupling agent further to improve the adhesive power of described tackiness agent to the sheet glass of such as panel etc.
Silane coupling agent can be typical one well known by persons skilled in the art.Such as, silane coupling agent can comprise and is selected from as epoxidised silicon compounds such as 3-glycydoxy Trimethoxy silane, 3-glycydoxy methyl dimethoxysilane, 2-(3,4-epoxycyclohexyl) ethyl trimethoxy silanes; As the silicon compound containing unsaturated polymerizable group of vinyltrimethoxy silane, vinyltriethoxysilane and (methyl) acryloxypropyl Trimethoxy silane; As the silicon compound containing amino of 3-TSL 8330, N-(2-amino-ethyl)-3-TSL 8330, N-(2-amino-ethyl)-3-amino propyl methyl dimethoxysilane etc.; 3-r-chloropropyl trimethoxyl silane; Deng at least one, but to be not limited thereto.Preferably, silane coupling agent is epoxidised silicon compound, and because this silane coupling agent improves the adhesive power of binder film to adherend, binder film can present the weather resistance of improvement.
Based on (methyl) acrylic copolymer of 100 weight parts, the content of silane coupling agent can be about 0.01 weight part to about 5 weight parts, and such as, about 0.01 weight part is to about 1 weight part, and such as, about 0.1 weight part is to about 1.0 weight parts.Within the scope of this, binder film can present the adhesive power to liquid crystal panel excellence, and (methyl) acrylic copolymer can present excellent stability in storage.With solid content meter, the content of silane coupling agent in binder composition can be about 0.1wt% to about 10wt%, such as, and about 0.1wt% to about 1wt%.Within the scope of this, binder film can present the adhesive power to liquid crystal panel excellence, and (methyl) acrylic copolymer can present excellent stability in storage.
Binder composition for polarization plates can comprise solvent further.Described solvent can be any solvent that can dissolve (methyl) acrylic copolymer and linking agent.Such as, solvent can comprise methylethylketone, or the solvent mixture containing methylethylketone, but is not limited thereto.
After this, the polarization plates according to an embodiment of the invention is described in detail with reference to Fig. 1.Fig. 1 is the viewgraph of cross-section of the polarization plates according to an embodiment of the invention.
With reference to Fig. 1, the polarization plates 100 according to an embodiment can comprise: polarizer 110; Be formed in the first blooming 120 on the upside of polarizer 110; Be formed in the second blooming 130 on the downside of polarizer 110; With the binder film 140 for polarization plates be formed on the downside of the second blooming 130, wherein, binder film 140 can comprise the binder film for polarization plates according to an embodiment of the invention.
No matter which kind of preparation method, polarizer is all by any polyvinyl alcohol film preparation.Such as, polarizer can be the polyvinyl alcohol film of modification, the polyvinyl alcohol film of such as part formamide, acetoacetyl modified polyvinyl alcohol film etc.Polyvinyl alcohol film can have 1,500 to 4, the polymerization degree of 000, and within the scope of this, polyvinyl alcohol film can be used as polarizer, and presents suitable optical property when being prepared to polarizer.By with iodine or dichroic dye dyeing polyvinyl alcohol film, stretch in a certain direction subsequently and prepare described polarizer.Particularly, by swelling, dyeing and stretch preparation described polarizer.The method usually known by those skilled in the art carries out each process.
Described polarizer can have the thickness of 10 μm to 50 μm, but is not limited thereto.
Each at least one comprised in protective membrane and optical compensation films in first blooming and the second blooming.Described protective membrane is non-delayed film and can comprises Mierocrystalline cellulose (comprising triacetyl cellulose (TAC) etc.); cyclic olefin polymer (COP) (comprising amorphous cyclic olefin polymer etc.); polyester (comprising poly-(methyl) acrylate, polycarbonate, polyethylene terephthalate (PET) etc.); polyethersulfone; polysulfones; polymeric amide; polyimide, polyolefine; polyacrylic ester; polyvinyl alcohol; polyvinyl chloride, polyvinylidene dichloride, and their mixture.Protective membrane has the thickness of 10 μm to 200 μm, preferably, and about 30 μm to 120 μm, but be not limited thereto.
Optical compensation films is the film for generation of postponing, and can be typical phase shift films.Phase shift films can be any phase shift films be typically used in polarization plates.Such as, phase shift films can comprise cyclic olefin polymer, polycarbonate, poly-(methyl) acrylate and polyester film.
By the dry and/or aging described binder composition for polarization plates, with after fixing, carry out the binder film for the preparation of polarization plates.Drying and/or aging 24 little of 96 hours can be carried out at 30 DEG C to 35 DEG C, but be not limited thereto.
Binder film for polarization plates can have the thickness of 5 μm to 100 μm.
Although do not show in FIG, according to the polarization plates of an embodiment of the invention by sticking to panel (such as, panel of LCD) for the binder film of polarization plates.
Light leak can be made when adhering to panel to minimize according to the polarization plates of embodiment, and there is the light leak value (Δ L) of 0 to 0.4, be preferably 0 to 0.3, such as, 0 to 0.1, represented by equation 3:
[equation 3]
ΔL＝[(a+b+d+e)/4]/c–1]
(a, b, d and e are respectively the stacking brightness having the mid point in every face of the panel of polarization plates on it, and c stackingly on it has the brightness of the central point of the panel of polarization plates before reliability testing).
In light leak is measured, sample (i.e. polarization plates) is placed 250 hours at 85 DEG C, or place 250 hours under as 60 DEG C/90%RH of humidity resistance condition, then place 1 hour or more of a specified duration at 25 DEG C.
According to an embodiment of the invention, optical display can comprise the binder film for polarization plates.Described optical display can comprise liquid-crystal display, such as TFT-LCD etc., but is not limited thereto.
After this, with reference to Fig. 2, the optical display according to an embodiment of the invention is described.Fig. 2 is the viewgraph of cross-section of the optical display according to an embodiment of the invention.
With reference to Fig. 2, the optical display 200 according to an embodiment of the invention can comprise panel 210; With the polarization plates 220 be formed on the upside of panel 210, wherein polarization plates 220 can be the polarization plates according to an embodiment of the invention.Although the polarization plates being formed in the downside of described panel does not show in fig. 2, optical display can comprise the polarization plates of the downside being formed in described panel further.Here, the described polarization plates be formed on the downside of described panel can be the polarization plates according to an embodiment.
After this, the present invention is illustrated in greater detail with reference to some embodiments.But, it should be noted provide these embodiments only for illustration of object, and should not be construed as restriction the present invention.
Preparation example 1
In the reactor of the 1L with thermometer, reflux exchanger and agitator, place n-butyl acrylate and the solvent (ethyl acetate of 40 weight parts and the methylethylketone of 45 weight parts) of 97 weight parts, at 65 DEG C, carry out nitrogen replacement 30 minutes subsequently.Then, with the diluted ethyl acetate of 2 weight parts as 2,2'-Diisopropyl azodicarboxylates of 0.06 weight part of initiator, then added in reactor.Then, in reactor, drip the vinylformic acid of 2 weight parts and the HEMA of 1 weight part, carry out reaction 6 hours when the temperature of reactor maintains 65 DEG C subsequently.Then, reactor heating to 70 DEG C, thus carry out reaction 2 hours.After completion of the reaction, with the diluted ethyl acetate gained mixture of 130 weight parts, thus obtain the acrylic copolymer with the weight-average molecular weight of 900,000g/mol.
Preparation example 2
In the reactor of the 1L with thermometer, reflux exchanger and agitator, place the ethyl acetate as solvent of the n-butyl acrylate of 97 weight parts, 85 weight parts, at 65 DEG C, carry out nitrogen replacement 30 minutes subsequently.Then, with the diluted ethyl acetate of 2 weight parts as 2,2'-Diisopropyl azodicarboxylates of 0.04 weight part of initiator, then put it in reactor.Then, in reactor, drip the vinylformic acid of 2 weight parts and the HEMA of 1 weight part, carry out reaction 6 hours when the temperature of reactor maintains 65 DEG C subsequently.Then, reactor heating to 70 DEG C, thus carry out reaction 2 hours.After completion of the reaction, with the diluted ethyl acetate gained mixture of 130 weight parts, thus obtain the acrylic copolymer with the weight-average molecular weight of 1,100,000g/mol.
Preparation example 3
In the reactor of the 1L with thermometer, reflux exchanger and agitator, place the n-butyl acrylate of 97 weight parts, the vinylformic acid of 2 weight parts, the HEMA of 1 weight part and the ethyl acetate of 60 weight parts and the methylethylketone as solvent of 25 weight parts, subsequently at 65 DEG C through nitrogen replacement 30 minutes.Then, with the diluted ethyl acetate of 2 weight parts as 2,2'-Diisopropyl azodicarboxylates of 0.04 weight part of initiator, then reactor is put into.Then, carry out reaction 6 hours when the temperature of reactor maintains 65 DEG C, reactor heating to 70 DEG C subsequently, thus carry out reaction 2 hours.After completion of the reaction, with the diluted ethyl acetate gained mixture of 130 weight parts, thus obtain the acrylic copolymer with the weight-average molecular weight of 1,000,000g/mol.
Measure the retention time of the acrylic copolymer of preparation example 1 to 3.For measuring retention time, by being coated with (methyl) acrylic copolymer on release film, at room temperature dry subsequently, and by prepared coating in the baking oven of 90 DEG C dry 4 minutes again.By coating stack, in polarization plates, (stacked body of TAC-polarizer-TAC) is then cut into the sample with 15mm × 120mm (width × length) size, incites somebody to action the part adheres of wherein 15mm × 15mm (width × length) subsequently on a glass.When by use universal testing machine (UTM) to its apply constant power (750gf) carry out peel sample time, measure until sample start be separated time (unit: second).Result is displayed in Table 1.
Table 1
| ? | Preparation example 1 | Preparation example 2 | Preparation example 3 |
| Weight-average molecular weight (g/mol) | 900,000 | 1,100,000 | 1,000,000 |
| Retention time (second) | 300 | 350 | 420 |
| Functional group arranges | Functional group is evenly distributed | Functional group is evenly distributed | The uneven arrangement of functional group |
As shown in table 1, acrylic copolymer due to preparation example 1 and 2 has the retention time shorter than preparation example 3, susceptible of proof, compared with the acrylic copolymer of preparation example 3, in the acrylic copolymer of preparation example 1 and 2, functional group (hydroxyl, carboxylic acid group) is evenly arranged in copolymer chain.The multipolymer that wherein functional group is evenly distributed can have short retention time, and due to the height interaction between the part containing relatively a large amount of functional groups in multipolymer, the multipolymer of the wherein uneven arrangement of functional group can have long retention time.
Embodiment 1
The acrylic copolymer of the preparation example 1 of 100 weight parts and the methylethylketone as solvent of 3 weight parts are added in reactor, stirs subsequently.Then, by isocyanate crosslinking 1, metal-chelating linking agent (aluminium acetylacetonate) and silane coupling agent (KBE-403, Shinetsu chemical company) add respectively in reactor with amount listed in table 2, stir subsequently, thus for the preparation of the binder composition of polarization plates.
Embodiment 2 and 3
Except change the amount of metal-chelating linking agent according to table 2 except, in the same manner as example 1 for the preparation of the binder composition of polarization plates.
Comparative example 1 and 3
Except change the amount of (methyl) acrylic copolymer and linking agent according to table 2 except, in the same manner as example 1 for the preparation of the binder composition of polarization plates.
Table 2
* isocyanate crosslinking 1: the polyisocyanate crosslinking agent of modification.With the Coronate L (Nippon Polyurethane company limited) of dilution with toluene 100 weight part of 50 weight parts, then the propyl alcohol of 2 weight parts is added in the Coronate L of dilution, at 50 DEG C, carry out reaction 3 hours subsequently.Then, use FTIR to determine the reduction of isocyanate group, thus prepare isocyanate crosslinking 1 (some isocyanate group are by end-blocking).
* isocyanate crosslinking 2: with the Coronate L (Nippon Polyurethane company limited) of dilution with toluene 100 weight part of 50 weight parts, thus prepare isocyanate crosslinking 1 (isocyanate group is not by end-blocking).
Evaluate the following performance of the binder layer for polarization plates and the polarization plates prepared in embodiment and comparative example.Result is displayed in Table 3.
Table 3
As shown in table 3, although based on storage modulus and gel fraction, binder film according to the present invention is gravity die binder film, but because it comprises evenly distributed (methyl) acrylic copolymer of wherein reactive functional groups, the isocyanate crosslinking of end-blocking and metal-chelating linking agent, this binder film at high temperature has high-peeling strength and presents the weather resistance of improvement.In addition, binder film according to the present invention effectively suppresses the light leak of polarization plates due to the high storage modulus determined according to 60 μm or less creep(ing) distance and high adhesive power, and present good cutability and good can re-workability.Therefore, the invention provides the binder film for polarization plates, this binder film is gravity die binder film, high-peeling strength is presented due to the good fluidity under high temperature and/or super-humid conditions and wettability, impact at high temperature or Low Temperature Thermal and do not suffer the disengaging on the edge of polarization plates or wrinkling under wet heat condition, and therefore presenting excellent weather resistance.The invention provides the binder film for polarization plates, this binder film is gravity die binder film, and can impact and the pressure that produced by the contraction or expansion of polarization plates by control under wet heat condition and suppress light leak at high temperature or Low Temperature Thermal.The invention provides the binder film for polarization plates, this binder film is gravity die binder film, and presents excellent cutability and can re-workability.
On the contrary, only use the binder film without the comparative example 1 of the isocyanate crosslinking of end-blocking to present poor weather resistance, and bubbled and depart from.
In addition, the binder film of comparative example 2, wherein (methyl) acrylic copolymer has about 1,000, the weight-average molecular weight of 000g/mol, even if functional group is evenly distributed in described (methyl) acrylic copolymer, the binder film of comparative example 2 also presents poor weather resistance.And the binder film comprising the comparative example 3 of (methyl) acrylic copolymer of the uneven arrangement of wherein functional group is departed from and is caused the light leak of polarization plates.
(1) stripping strength (gf/25mm): measure the 180 ° of stripping strengths between binder film and glass substrate being used for polarization plates according to JIS2107.Each binder composition for polarization plates of embodiment and comparative example is coated on polarization plates, under 35 DEG C and the steady temperature of 45%RH and the condition of humidity aging 2 days subsequently, thus prepare the polarization plates sample it being formed with the binder film for polarization plates.Here, described polarization plates can be the polarization plates of the preparation by stacking triacetyl cellulose (TAC) on polarizer two surfaces.Sample is cut into the size of 25mm × 210mm × 280 μm (width × length × thickness), and the sample layer of 25mm × 140mm (width × length) area is pressed in sheet glass (25mm × 140mm, width × length) on to make described binder film lamination on the glass substrate, suppress under 50 DEG C and 3.5atm subsequently.Then, sample is placed 1 hour at 25 DEG C, thus for the preparation of measuring the sample of stripping strength.Under 30kgf load sensor, binder film and sheet glass are connected to the upper side and lower side fixture respectively, peel off with the draw speed of 300mm/min with the angle of 180 ° at 25 DEG C subsequently, thus measuring load when peeling off.Here, load placement measured after 60 minutes is as stripping strength B.Stripping strength ratio is calculated by equation 1.
(2) storage modulus (Pa): the binder composition respectively for polarization plates is coated on polyethylene terephthalate release film, at 120 DEG C dry 3 minutes subsequently, thus the binder layer that preparation 20 μm is thick.The binder layer of which floor solidification stacking, to form the thick adhesive sheet of 1mm, is then cut into the circular sample (use parallel plate fixtures) with 8mm diameter, thus prepares sample.Measure storage modulus from 0 DEG C to 120 DEG C under using the frequency of storage modulus tester (Physica, Anton Paar company limited) strain 10% and 10Hz, and obtain the storage modulus at 30 DEG C.
(3) gel fraction (%): the binder composition respectively for polarization plates is coated on polyethylene terephthalate release film, at 120 DEG C dry 3 minutes subsequently, thus the binder layer that preparation 20 μm is thick.After coating, binder composition is placed 1 hour under 35 DEG C and 45%RH, thus obtain the tackiness agent of 0.5g.Then, be wound around described binding agent with the wire cloth (W1) of having weighed in advance, to make described tackiness agent not spill, weigh (W2) subsequently, then tackiness agent and wire cloth put into sample bottle.Then, in sample bottle, add 50cc ethyl acetate, at 25 DEG C, tackiness agent and wire cloth are placed 1 day subsequently.Then, at 100 DEG C, drying containing the wire cloth 12 hours of tackiness agent, should be weighed (W3) to this wire cloth containing tackiness agent subsequently.According to equation 2 calculated for gel mark.
< equation 2>
Gel fraction (%)=(W3-W1)/(W2-W1) × 100
(wherein W1, W2 and W3 by such as being defined in above-mentioned detailed description)
(4) transparency: the binder composition respectively for polarization plates is coated on polyethylene terephthalate release film, at 120 DEG C dry 3 minutes subsequently, thus the binder layer that preparation 20 μm is thick.Then, by naked eye binder layer.Be rated for " transparent " without fuzzy and be fuzzyly rated for " opaque ".
(5) creep(ing) distance ((μm): the size polarization plates of preparation in the measurement of (1) stripping strength being cut into 15mm × 120mm (width × length).Then, by the polarization plates lamination of 15mm × 15mm (width × length) area on a glass, suppress under 50 DEG C and 3.5atm subsequently.Then, this polarization plates is placed 3 days at 25 DEG C, thus prepares sample.This sample is tightly fixed on universal testing machine (UTM), subsequently under the constant force of 2250gf dilatory described sample 1000 seconds to measure the creep(ing) distance of binder film.
(6) light leak: the size polarization plates prepared of same mode in measuring with (1) stripping strength being cut into 100mm × 125mm (width × length), subsequently by this samples stick on two surfaces of LCD element to make the axis of homology of two surperficial samples orthogonal.Sample is placed 500 hours at 70 DEG C, subsequently in darkroom at room temperature operating panel with by naked eye light leak.
◎: the uneven Transmission light not occurring such as light leak on upper/lower/left side lateral edges
O: be difficult to by bore hole the uneven Transmission light determining such as light leak on upper/lower/left side lateral edges
Δ: the uneven Transmission light having slight such as light leak on upper/lower/left side lateral edges
X: the uneven Transmission light occurring serious such as light leak on upper/lower/left side lateral edges
(7) weather resistance: the size polarization plates prepared in same mode in the measurement of (1) stripping strength being cut into 100mm × 125mm (width × length).Then, by this samples stick in LCD element, suppress under 50 DEG C and 3.5atm subsequently.Carry out 200 circular treatment to described sample, each process is included in the process under dry heat condition, namely, at 85 DEG C 250 hours, the process under wet heat condition, namely under 60 DEG C and 90%RH 250 hours, with the process under thermal shock conditions, namely at-40 DEG C 30 minutes and at 85 DEG C 30 minutes.Then, sample is placed 1 hour at 25 DEG C.Confirm whether to occur the disengaging of binder film and wrinkling on the edge of polarization plates.Judgement criteria is as follows.
O: without bubbling, peel off and departing from
Δ: slight foaming, stripping and disengaging
X: serious foaming, stripping and disengaging
(8) can re-workability: size polarization plates prepared by same mode in measuring with (1) stripping strength being cut into 200mm × 250mm (width × length), subsequently by described samples stick in LCD element.Then, sample is placed 4 hours in loft drier at 50 DEG C, at room temperature place 30 days subsequently.
O: polarization plates can be stripped and the situation on liquid crystal cell do not transferred to by tackiness agent
Δ: when polarization plates can be stripped, in adhesive transfer to described liquid crystal cell and situation about retaining thereon
X: the situation that polarization plates can not be stripped
Should understand and can make various amendment, change, change and the equivalent form of value not deviating under spirit and scope of the invention.
Claims (19)
1. the binder film for polarization plates, described binder film is formed by composition, described composition comprises (methyl) acrylic copolymer and linking agent, and described binder film has the stripping strength ratio of about 6 or larger, and described stripping strength is than being represented by equation 1:
[equation 1]
Stripping strength ratio=B/A
Wherein, A be when at 25 DEG C with the angle of 180 ° and use 30kgf load sensor to be peeled off from glass substrate by described binder film with the draw speed of 300mm/min time stripping strength, in units of gf/25mm; And
B be when described binder film is placed at 85 DEG C 60 minutes then at 85 DEG C with the angle of 180 ° and use 30kgf load sensor to be peeled off from described glass substrate by described binder film with the draw speed of 300mm/min time stripping strength, in units of gf/25mm
The polarization plates comprising described binder film is wherein formed on the sample on the upper surface of described glass substrate and measures described stripping strength ratio.
2. binder film according to claim 1, wherein, described binder film has the gel fraction of about 70% or more, and described gel fraction is represented by equation 2:
[equation 2]
Gel fraction (%)=(W3-W1)/(W2-W1) × 100
Wherein W1 is the weight of wire cloth;
W2 is the gross weight of described wire cloth and tackiness agent, described gross weight is used for the binder composition 3 minutes of polarization plates by dry at 120 DEG C and placed described binder composition 1 hour under 35 DEG C and 45%RH, is then placed on wire cloth and obtains; And
W3 is the gross weight of described wire cloth and described tackiness agent, wherein will be used for the binder composition 3 minutes of polarization plates and the tackiness agent placement of placing described binder composition 1 hour under 35 DEG C with 45%RH and obtaining is placed in sample bottle on a wire mesh and by described tackiness agent together with described wire cloth by dry at 120 DEG C, ethyl acetate is added subsequently in described sample bottle, then place 1 day at 25 DEG C, at 100 DEG C dry 12 hours subsequently, and obtain described gross weight.
3. binder film according to claim 1, wherein, described binder film has the stripping strength A of 200gf/25mm to 500gf/25mm, and the stripping strength B of 1500gf/25mm to 3000gf/25mm.
4. binder film according to claim 1, wherein, described (methyl) acrylic copolymer comprises and the hydroxyl that be connected to copolymer chain in and/or carboxylic acid group evenly distributed with predetermined space.
5. binder film according to claim 1, wherein, be polymerized by (methyl) Acrylic Acid Monomer introduced containing non-reacted functional group, subsequently by instillation containing reactive functional groups (methyl) Acrylic Acid Monomer, described (methyl) acrylic copolymer of preparation.
6. binder film according to claim 1, wherein, described (methyl) acrylic copolymer has the weight-average molecular weight of 1,000,000g/mol or less.
7. binder film according to claim 1, wherein, described linking agent comprises the polyisocyanate crosslinking agent of modification and the mixture of metal-chelating linking agent.
8. binder film according to claim 7, wherein, the polyisocyanate crosslinking agent of the standby described modification by some isocyanate group systems of the multifunctional polyisocyanate crosslinking agent of end-blocking.
9. binder film according to claim 7, wherein, described metal-chelating linking agent comprises aluminium Chelating agent.
10. binder film according to claim 1, comprising: at least one metal be selected from aluminium, iron, copper, zinc, tin, titanium, nickel, antimony, magnesium, vanadium, chromium and zirconium of 0.1wt% to 10wt%.
11. binder films according to claim 7, the polyisocyanate crosslinking agent of modification described in wherein said composition and the weight ratio of described metal-chelating linking agent are 1 to 6.
12. binder films according to claim 7, the polyisocyanate crosslinking agent of modification described in wherein said composition and the weight ratio of described metal-chelating linking agent are 3 to 6.
13. binder films according to claim 7, wherein based on (methyl) acrylic copolymer described in 100 weight parts, the content of the polyisocyanate crosslinking agent of described modification is 0.1 weight part to 20 weight part.
14. binder films according to claim 7, wherein based on (methyl) acrylic copolymer described in 100 weight parts, the content of described metal-chelating linking agent is 0.1 weight part to 10 weight part.
15. binder films according to claim 1, wherein, described composition comprises silane coupling agent further.
16. binder films according to claim 15, wherein based on (methyl) acrylic copolymer described in 100 weight parts, the content of described silane coupling agent is 0.01 weight part to 5 weight part.
17. binder films according to claim 1, wherein, described binder film to have at 30 DEG C 5 × 10
5pa to 9 × 10
5the storage modulus of Pa, the measurement from 0 DEG C to 120 DEG C under 10% strain and 10Hz frequency of described storage modulus.
18. 1 kinds of polarization plates, described polarization plates comprises the binder film for polarization plates according to any one of claim 1 to 17.
19. 1 kinds of optical displays, described optical display comprises polarization plates according to claim 18.
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| KR10-2013-0071894 | 2013-06-21 | ||
| KR20130071894 | 2013-06-21 | ||
| KR1020130153521A KR101665166B1 (en) | 2013-06-21 | 2013-12-10 | Adhesive film for polarizing plate, polarizing plate comprising the same and optical display apparatus comprising the same |
| KR10-2013-0153521 | 2013-12-10 |
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2003073638A (en) * | 2001-08-31 | 2003-03-12 | Nippon Synthetic Chem Ind Co Ltd:The | Self-adhesive composition |
| CN1740256A (en) * | 2004-08-23 | 2006-03-01 | 琳得科株式会社 | Pressure-sensitive adhesive composition used for polarized film |
| WO2012105341A1 (en) * | 2011-02-04 | 2012-08-09 | 日東電工株式会社 | Release agent, release material, and adhesive tape |
| CN102816544A (en) * | 2011-05-30 | 2012-12-12 | 第一毛织株式会社 | Adhesive composition, adhesive layer, optical member, and adhesive sheet |
| CN102816545A (en) * | 2011-06-09 | 2012-12-12 | 第一毛织株式会社 | Adhesive composition and optical component using same |
Family Cites Families (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2733180B2 (en) * | 1993-02-09 | 1998-03-30 | 東洋製罐株式会社 | Flexible packaging laminate, method for producing the same, and adhesive used therefor |
| TW312700B (en) | 1994-05-17 | 1997-08-11 | Sony Co Ltd | |
| US5754338A (en) * | 1996-04-01 | 1998-05-19 | Minnesota Mining And Manufacturing Company | Structured retroreflective sheeting having a rivet-like connection |
| JP4521520B2 (en) | 2003-08-06 | 2010-08-11 | 綜研化学株式会社 | Adhesive for low polarity film |
| JP5580069B2 (en) * | 2009-02-26 | 2014-08-27 | 日東電工株式会社 | Adhesive composition for surface protective film and use thereof |
| CN101899127B (en) | 2009-06-01 | 2012-07-25 | 钟文军 | Polyurethane modified acrylic resin and preparation method thereof |
| JP2011018806A (en) * | 2009-07-09 | 2011-01-27 | Sumitomo Bakelite Co Ltd | Film for semiconductor, and method of manufacturing semiconductor device |
| KR101293879B1 (en) | 2010-02-26 | 2013-08-07 | 주식회사 엘지화학 | Pressure sensitive adhesive composition |
| KR101813260B1 (en) | 2011-01-14 | 2018-01-02 | 삼성전자주식회사 | Patternable Adhesive Composition, Semi-conductive Package Using the Same, and Method of Preparing Semi-conductive Package |
| KR101374374B1 (en) * | 2011-08-11 | 2014-03-17 | 제일모직주식회사 | Adhesive Composition, Adhesive Film Comprising the Same, Method for Preparing the Adhesive Film and Display Member Using the Same |
| KR101566061B1 (en) * | 2012-12-27 | 2015-11-04 | 제일모직주식회사 | Adhesive film, adhesive composition for the same and display member comprising the same |
| KR101628435B1 (en) * | 2013-01-21 | 2016-06-08 | 제일모직주식회사 | Adhesive film, adhesive composition for the same and display member comprising the same |
-
2014
- 2014-06-19 US US14/309,795 patent/US9382456B2/en active Active
- 2014-06-20 CN CN201410279652.3A patent/CN104231952B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2003073638A (en) * | 2001-08-31 | 2003-03-12 | Nippon Synthetic Chem Ind Co Ltd:The | Self-adhesive composition |
| CN1740256A (en) * | 2004-08-23 | 2006-03-01 | 琳得科株式会社 | Pressure-sensitive adhesive composition used for polarized film |
| WO2012105341A1 (en) * | 2011-02-04 | 2012-08-09 | 日東電工株式会社 | Release agent, release material, and adhesive tape |
| CN102816544A (en) * | 2011-05-30 | 2012-12-12 | 第一毛织株式会社 | Adhesive composition, adhesive layer, optical member, and adhesive sheet |
| CN102816545A (en) * | 2011-06-09 | 2012-12-12 | 第一毛织株式会社 | Adhesive composition and optical component using same |
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Also Published As
| Publication number | Publication date |
|---|---|
| US20140378614A1 (en) | 2014-12-25 |
| CN104231952B (en) | 2017-05-17 |
| US9382456B2 (en) | 2016-07-05 |
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